Process of preparing 2-methyl oxazolidine-3-carboxylic esters



United States PROCESS OF PREPARING Z-METHYL OXAZOLI- DINE-3-CARBOXYLIC ESTERS Sidney Melamed, Philadelphia, Pa., assignor to Rohm & Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Application October 29, 1954 Serial No. 465,717

3 Claims. (Cl. 260-244) where n is an integer having a'value of 1 or 2, x is an integer having a value of 2 to 4, R is hydrogen, an alkyl group of 1 to 16 carbon atoms, a cyclohexyl group, or

V a vinyl group, R' is hydrogen or an alkyl group of 1 to 4 carbon atoms, R is hydrogen or a methyl group, R is hydrogen or a methyl group, R is hydrogen or an alkyl group of 1 to 4 carbon atoms, R is an aliphatic or alicyclic hydrocarbon group of saturated or ethylenically unsaturated types having 1 to 24 carbon atoms, an aryl, haloaryl, alkaryl, or aralkyl group of 6 to 24 carbon atoms, an alkyloxyalkyl, alkyloxyphenyl, phenoxyalkyl, alkylthioalkyl, alkylthiophenyl, phenylthioalkyl group containing 3 to 24 carbon atoms, a (polyoxyalkylene)- alkyl, (polythioalkylene)alkyl, (polyoxyalkylene)phenyl, or (polythioalkylene)phenyl group having 5 to 24 carbon atoms, a cyanoalkyl group of 2 to 24 carbon atoms, and an ethylsulfonylethyl group, B is a straight-chain, branched-chain, or cyclic alkylene group of 2 to 18 carbon atoms or a trior tetra-valent aliphatic hydrocarbon group of 3 to 18 carbon atoms, an alkyleneoxyalkylene, alkylenethioalkylene, (polyalkyleneoxy) alkylene or. (polyalkylenethio)alkylene group of 4 to 18 carbon atoms, a di-, tri-, or tetra-valent residue of benzene, of naphthalene, of indene, of diphenyl, of a diphenylalkane, or of a triphenylalkane.

In the compounds of Formula II, the polyvalent group B may be connected to two or more identical radicals represented within the brackets or one or more or all of such bracketed radicals may be difierent from at least one other such radical or from each other by virtue of the substitution of a different group for one or more or each of the several substituents represented by the symbols R,

R', R R and R In one class of preferred compounds having outstandsolvent properties, R, R and R are hydrogen, R

atent 2,920,075 Patented Jan. 5, 1960 and R are hydrogen or an alkyl group of l to 4 carbon '2 (III) R OCOCl or with a polychlorocarbonate of Formula IV in which formulas the symbols have the same definitions as given above, with the production of the esters of the invention, the yields are poor and the products require extensive purification, apparently because of the instability of the initial 2-methyloxazolidines andthe 2-methyltetra-' hydro'oxazines and their tendency to tautomerize. These initial compounds containing a secondary nitrogen atom are as a class difficult to prepare, unstable and tautomeric. In general, 2-methyloxazolidines and their 2- methyltetrahydrooxazine analogs exist 'as mixtures in varying proportions of the indicated compounds and their tautomeric Schifl base isomers. These conditions are illustrated by 2-methyloxazolidine itself which is obtained in poor yield by reacting ethanolamine with acetaldehyde, resinifies on standing and exists in the following equilibrium:

The unsubstituted oxazolidine and the unsubstituted tetrahydrooxazine analog are too unstable to be isolated.

The compounds of this invention are, however, stable compounds. The methyl group in the 2-position apparently contributes to a surprising extent to the stability of the new compounds. Nevertheless, the new compounds are highly reactive under suitable conditions as will be pointed out more particularly hereinafter.

The compounds of Formula I may be prepared by the reaction of a substituted chlorocarbonate of the Formula III above which is also known as a chloroformate and is recognized as a half-ester, half-acid chloride of carbonic acid, with a primary amine of the Formula V leads directly to the production of the new cyclic prodnets of this invention. It could not have been predicted this invention.

The present invention thus provides a preferred process for producing esters of Formulas I and II above in which the isolation of and/or reaction with a Z-methyloxazolidine or 2-methyltetrahydro-1,3-oxazine are avoided. The preferred processes produce the new compounds in high yield from readily available raw materials. 7

The conditions of the reactions for the preparation of the compounds'of this invention may vary widely. The temperature may be from 10 C. to 100 C. or more, preferably -l to 100 C. Reaction is preferably ef fected in the presence of a basic acceptor for the hydro gen chloride liberated, such as excess of the amine reactant, a tertiary organic base'such as pyridine, quinoline or triethylamine, or an inorganic base, such as NaOH, KOH, LiOI-I, Na CO K CO and the like. The reaction may be efiected Without a solvent or in an inert solvent, such as benzene, toluene, xylene, petroleum ether, ether, acetonitrile, or in a mixture of such a solvent with water. The chlorocarbonate or polychlorocarbonate is usually added to the amine; however, in certain cases the order of addition may be reversed or both compounds may be added together. The time required for the reaction varies from one to twenty-four hours though in general a reaction time of one to four hours is sufiicient. The product of the invention may then be recovered or isolated from the reaction medium and/or further purified by appropriate procedures, such as evaporation of solvents therefrom, crystallization or distillation of the product therefrom, depending on its nature.

The amines of Formula V that are used in effecting these reactions are readily obtained from the reaction of acetyleneunder pressure with the corresponding aminoalcohols as described by Reppe and others. Representative amines of Formula V that may be used in the practice of this invention are:

CH =CH0CH CH (on NH CH =CHOCH CH CH NH CH =CH0CH cm, CH NH CH' =CHOCH CH (C H NH CH =CHOCH C (CH CH NH CH =CHOC CH CH NH CH =CHOCH CH C H NH CH =CHOCH (CH CH) CH NH CH CHOCH(C H CH NH CH CHOCH C l-I CH NH CH =CHOCH C H CH NH CH =CHOCH C H 3 CH NH CH =CHOC( CH (C H CH NH Examples of the substituted chlorocarbonates of Formula III which are prepared from the corresponding alcohols or phenols and phosgene are chlorocarbonates in which the substituent may be methyl, ethyl, butyl, isobutyl, octyl, Z-ethylhexyl, dodecyl, octadecyl, tetracosanyl, allyl, 2-ethyl-2-hexenyl, oleyl, 10-undecenyl, cyclopentyl, cyclohexyl, Z-chloroethyl, S-cyanopentyl, methoxyethyl, ethoxyethyl, butoxyethyl, lauroxyethyl, ethoxyethoxyethyl, methylthioethyl, ethylthioethyl, laurylthioethyl, ethylsulfonylethyl, phenyl, methylphenyl, ethyl- 4 mula IV which are prepared from diols, polyols, or polyhydric phenols and phosgeneare:

oioooomomooool OlO0O(CH2)sOCOO1 (010 o o omonQ-o CICOOOH O (CHZO C 0 CD .CHaCH(CH2O O 0 CD3 L010 0 O --O OH:J V s" indicates saturation. 2

OCOC1 010 o 0 omQ-omo o 0 or 010 o 0 omQQ-omo oo 01 The compounds of this invention range from mobile liquids to solids. They are stable, organic-solvent-soluble, water-insoluble products which may be hydrolyzed by hot acids or bases. All of the compounds of thisinvention are characterized by having methyl in the 2- position of the heterocyclic ring, and at leastone hydrogen in the 4-position of said ring.

The new compounds are generally useful as solvents, swelling agents, and plasticizers for organic plastic materials, cellulose esters vand ethers, such as cellulose nitrate, acetate, etc. and ethyl. cellulose, etc. and especially polymers of monoethylenically-unsaturated cornpounds, such as homopolymers and copolymers of vinyl chloride, vinyl acetate, vinylidenechloride, chlorotrifiuoroethylene, ethylene, isobutylene, acrylonitrile (especially those containing to 100% of acrylonitrile and the'remainder of another monomer, e.g. vinyl acetate, vinyl pyridine, etc.) esters of acrylic or methacrylic acid,

. such as the methyl, ethyl, isopropyl, butyl, hexyl, cyclohexylyand t-octyl esters thereof. The low-molecular weight compounds of Formulas I and II, and especially of Formula I, include good solvents for producing solutions of polymeric materials, such as those mentioned above for molding, casting, extruding, or otherwise forming films, fibers, filaments or other shaped articles therefrom and also for use as adhesives, coating, impregnating or laminating compositions. The high molecular weight compounds of Formulas Iand II and especially those of Formula II serve as permanent plasticizers for polymeric materials especially of the types mentioned. All of the materials of the invention, regardless of .molecular weight can be used as swelling agents to aid the dyeing of polymeric materials, such as those mentioned above.

One class of compounds preferredfor certain applications are those of Formula I in which R is an aliphatic,

alicyclic or aralkyl group or such a group containing the hetero-atoms oxygen or sulfur. Members of this class are useful as anti-convulsants, solvents, insecticides, fungicides, insect repellents, and plasticizers.

A second preferred class of compounds are those of Formula I in which R is an aryl, alkaryl, or substituted aryl group. These compounds are useful as herbicides, plant-growth regulators, plasticizers and solvents.

A third class of preferred compounds are the polyheterocyclics of Formula II. These compounds find use as high-boiling solvents, permanent plasticizers and modifiers of aminoplast resins.

The heterocyclic oxazolidine or tetrahydrooxazine group or groups common to all of the compounds of this invention contribute important and unexpected properties thereto. For example, they impart reactivity to these compounds for other reactive materials such as ureas, aldehydes, melamines, epoxides, and the like, particularly in the presence of acid or acidic-type catalysts. Reaction with these compounds may sometimes involve opening of the ring or rings of the compounds of the invention. The heterocyclic nature of the compounds contributes to the useful physiological or pesticidal activity of numerous of the compounds of the invention. Additionally the heterocyclic groups impart particular and unpredictable solubility relationships contributing to compatibility in applications involving plasticization or compounding of resins, oils, and the like. The-heterocyclic nature of the compounds is important in other ways but obviously forms an integral and indispensable part of the invention.

Specific embodiments of these compounds and their utility are more fully described in the succeeding examples.

Example I A mixture is prepared by adding 87.1 g. (1 mole) of 2-aminoethyl vinyl ether and 150 ml. of toluene to a solution prepared by dissolving 83 g. (0.6 mole) of potassium carbonate in 150 ml. of water. This mixture is cooled to C. by means of a Dry-Ice/isopropanol bath and treated dropwise with 104 g. (1.1 moles) of methyl chlorocarbonate with efiicient stirring, the addition being completed in 2 /2 hours and the temperature being maintained at l0 to C. during the entire addition and then allowed to rise to 25 to 30 C. The mixture is filtered, the salt cake is washed with toluene and the combined liquids are transferred to a separatory funnel and the water layer is removed. The toluene solution is washed with several portions of ice water and then dried with anhydrous magnesium sulfate and potassium carbonate. The solution is concentrated and the residue distilled through a small Vigreaux column. The product amounting to 92 g. is isolated as a colorless liquid, B.P. 90 to 98 C./ 18 mm. Hg. Redistillation gives an analytical sample, B.P. 91 to 94 C./l8 mm. Hg, N (20 C.) 1.4468, containing 49.61% carbon, 7.38% hydrogen, 9.6% nitrogen. The theoret- 'ical values for 3-carbomethoxy-2-methyl-1,3-oxazolidine (the methyl ester of Z-methyl-1,3-oxazolidine-3-carboxylic acid) are 49.6% carbon, 7.59% hydrogen and 9.66% nitrogen. The compound does not absorb iodine in the standard test for unsaturation. The compound when examines spectroscopically shows no absorption at 6.2 or 122g in the infrared.

This compound is formulated as a 10% dust in clays, such as Pyrax and Diluex and applied to potato and bean plants. A 50% kill of bean beetle larvae is obtained with no foliage injury when applied at 38 lbs./ acre.

The compound is soluble in acetone, monobutyl ether of ethylene glycol and xylenes, such as Han 132 (a commercial xylene solvent). It is insoluble in water but is hydrolyzed with liberation of methanol by warming,

carbomethoxy-Z-methyl-1,3-oxazolidine has a low oral toxicity in rats, LD 800 mg./kilogram, and shows a mild but useful level of anti-convulsant activity.

This methyl ester of Z-methyl-1,3-oxazolidine-3-carboxylic acid is of particular interest as a spinning solvent for polymers and copolymers of acrylonitrile. For ex ample, a solution may readily be prepared by heating a copolymer of a mixture of 75 parts of acrylonitrile and 25 parts of ethyl acrylate in the ester of this example. A fiber is formed by extruding this dope through a spinneret into a hot, aqueous, regenerating bath. Similarly films may be prepared.

The compound is also useful as a special solvent in the preparation of lacquers and in the formulation of paint and lacquer removers.

The compound is a fungicide giving kill of either Monilinia fructicola or Stemphylium sarcinaeforme at 1% concentration.

Example 2 1.4413. It contains 52.99% carbon, 8.39% hydrogen and 8.6% nitrogen. The calculated values for 3-carbethoxy-2-methyl-l,3-ox-azolidine are 52.8% carbon, 8.18% hydrogen and 8.81% nitrogen. The compound does not absorb iodine in'a standard test for unsaturation and it shows no absorption at 6.2 or 12.2,u, in the infrared.

This compound is a versatile solvent and is soluble in methanol, acetone, monobutyl ethers or ethylene glycol and petroleum ether and insoluble in water. The compound is useful as a leveling agent and flow control agent in the formulation of lacquers and enamels. It is useful as the sole constituent of paint and lacquer removers or may be used in combination with other solvents such as hydrocarbons, ketones, lactones or esters in the formulation of such removers.

When applied to plants at 1 part in 400 the compound gives a 70% kill of aphids with little or no foliage injury. The compound is also a fungicide giving 100% control of both Monilinia fructicola and Stemphylium sarcinaeforme at the 1% level with no evidence of phytotoxicity when tested on tomato plant foliage.

The compound is a solvent for polymers and copolymers of acrylonitrile and as such is useful in the preparation of solutions for the spinning of fibers or films by regeneration. The compound is also a solvent for cellulose esters such as cellulose acetate or butyrate or a mixed ester such as cellulose acetate/butyrate.

Example 3 By the procedure of Example 1 there is condensed 32.2 g. (0.34 mole) of ethyl chlorocarbonate and 34 g. (0.34 mole) of 2-amino-1-methylethyl vinyl ether in the presence of 30.4 g. (0.22 mole) of potassium carbonate, 35 ml. of water and 100 ml. of toluene. The addition is effected over a period of 2 hours at -15 to 5 C The product, 34.8 g., is isolated as a colorless oil, B.P. 52 to 53 0/09 to 1.0 mm. Hg, N (19 C.) 1.4395, containing by analysis 55.45% carbon, 8.73% hydrogen and 8.14% nitrogen. This compares with the values 55.55% carbon, 8.68% hydrogen and 8.1% nitrogen calculated for 3 carbethoxy 2,5 dimethyl 1,3 oxazolidine. The product has a negligible iodine number and shows no .absorption at 6.2 or 12.2, in the infrared.

The compound is soluble in most organic solvents, in-

eluding alcohols, such as methanol, ethanol, and isopropanol, ketones, such as'acetone and dioxane, acetonitrile, nitroparaflins such as nitroethane, dimethylforrnamide, dimethylacetamide, and hydrocarbons, such as benzene, toluene, and xylenes, but it is'insoluble in water. It has a low oral toxicity and is active as a mild anti-convulsive.

The compound is a fungicide. When applied at a concentration of 1% (in an aqueous emulsion of a Xylene solution thereof), it gives 100% control of either Monilinia fructicola or Stemphylium sarcinaeforme organisms (supra) with no foliage injury to tomato plants.

Example 4 By'the procedure of Example 1, there is condensed 54.25 g. (0.5 mole) of ethyl chlorocarbonate and 57.7 g. (0.5 mole) of Z-amino'outyl vinyl ether in the presence of 41.5 g. (0.3 mole) of potassium carbonate, 50 ml. of water and 150 ml. of toluene. The product, amounting to 55 g., is isolated as a water-white liquid with a pleasant, ester-like odor, B.P. 75 to 80 C./ 2.5 to 2.8 mm. Hg, N (20.5 C.) 1.4432. Analysis indicates the presence of 57.10% carbon, 9.08% hydrogen and 7.42% nitrogen; the 3-carbethoxy-2-methyl-4-ethyl- 1,3-oxazolidine obtained theoretically requires 57.7% carbon, 9.09% hydrogen and 7.48% nitrogen. The compound is soluble in acetone, monobutyl ether of ethylene glycol, petroleum hi-fiash naphtha and insoluble in water. The compound has a negligible iodine number.

The compound is both a stomach poison and a contact insecticide. A dust in a Pyrax-Diluex mixture gives a 40% kill of bean beetles at approximately 40 lb./acre while a 25% solution in acetone when emulsified in water at 1 part in 800 gives a 60% kill of red spider mites with no foliage injury. The compound is also a nonphytotoxic fungicide giving 100% kill of Monilinia fructicola or Stemphylium sarcinaeforme with no injury to tomato plants at 1% concentration.

Example 5 (a) By the procedure of Example 1, there is condensed 32.6 g. (0.3 mole) of ethyl chlorocarbonate and 30.3 g. (0.3 mole) of 3-aminopropyl vinyl ether in the presence of 27.6 g. (0.2 mole) of potassium carbonate, 35 ml. of water and 150 ml. of toluene. The product amounting to 26 g. is obtained as a water-white liquidof ester-like odor, B.P. 122 to 127 C./31 mm. Hg, containing by analysis 55.53% carbon, 8.72% hydrogen and 7.91% nitrogen. The product corresponds in structure to 3- carbethoxy-2-methyltetrahydro-1,3-oxazine for which the calculated values are 55.5% carbon, 8.73% hydrogen and 8.1% nitrogen. The index of refraction, N (22 C.), is 1.4531.

The compound has a negligible iodine number and shows no absorption at 3.0, 6.2 or 12.2 microns in the infrared spectrum. The compound is soluble in both polar and non-polar organic solvents including those mentioned in Example 3, but it is insoluble in water.

The compound shows a low oral toxicity and is active as an anti-convulsant.

The compound is a solvent for cellulose esters, including cellulose acetate and cellulose acetate-butyrate and ac-rylonitrile copolymers containing at least 50% acrylonitrile. It is a good solvent for lacquers and paints.

(b) The procedure of part (0) hereof is followed except that the vinyl ether is replaced with 0.3 moleof 2- amino-l-methyl-l-butyl vinyl ether in one run and with 0.3 mole of 2-aminohexyl vinyl ether in another run.

Products are obtained having similar properties.

Example 6 ence of 58 g. (0.42 mole) of potassium carbonate,'100

m1. of water and 100 ml. of toluene; Theproduct, a light yellow liquid, amounts to 49.5 g;, having 'a B.P of 92 to 94 C./l.5 mrn. Hg, N (255 C.) 1.4629, containing 56.07% carbon, 7.69% hydrogen, and 8.13% nitrogen. These values agree with the 56.2% carbon, 7.6% hydrogen and 8.0% nitrogen calculated for 3- carballyloxy-2methyl-1,3-oxazolidine. The compound is soluble in acetone and Insecti Sol (a high-flash point kerosene) and insoluble in water.

The compound is useful as an insecticide showing a high residual toxicity to the housefly. Applied at 75 mg./sq. ft. it gives 100% kill after six hours and at 37 mg./sq. ft., it still gives kill. It is elfective spatially as shown by tests in screened cages giving 60% kill at 150 mg./sq. ft.

The compound is fungitoxic to Monilim'a fructicola and Stemphylium sarcinaeforme showing no injury to tomato plants at a concentration of 1%.

Example 7 Benzyl chlorocarbonate, 47 g. (0.27 mole), and aminoethyl vinyl ether,24 g. (0.27 mole), are condensed in the presence of 34.5 g. (0.25 mole) of potassium carbonate, 60 ml. of water, and 60 ml. of toluene by the procedure of Example 1. The distilled product, amounting to 22.3 g., is a light yellow oil, B.P. 119 to 120 C./0.5 mm. Hg, N (255 C.) 1.5200, containing by analysis 65.77% carbon, 6.88% hydrogen, and 6.34% nitrogen. The material is thus the benzyl ester of 2- methyl-1,3-oxazolidine-3-carboxylic acid for which the calculated values are 65.2% carbon, 6.7% hydrogen and 6.3% nitrogen. The compound is soluble in acetone and monobutyl ether of ethylene glycol and insoluble in water.

The product is useful as a contact insecticide. A 25% concentrate prepared in Han 132 (an aromatic, high-boiling solvent) when diluted and emulsified in water to 1:800 and applied to infested plants gives a 65% kill of bean aphids and an 83% kill of red-spiders with no injury to the foliage. This material is useful as an anticonvulsant and has a low oral toxicity in rats, LD 800 mg./kilogram.

Example 8 (a) cyclohexyl chlorocarbonate (one mole) and 2- amino-l-cyclohexylethyl vinyl ether (one mole) are condensed by the procedure of Example 1 in the presence of potassium carbonate (0.6 mole), ml. of water and 250 ml. of toluene. The product is isolated by distillation as a light yellow oil corresponding in structure to the cyclohexyl ester of Z-methyl-S-cyclohexyl-l,3-oxazolidine-3-carboxylic acid.

This material is useful as a mosquito-repellent. When applied to the forearm it repels both Ae'a'es aegypti and Anopheles quadrimacalatus. Cloth treated with the compound is repellent to various types of mosquitoes for periods as long as 10 days.

(b) In a like manner, cyclopentyl chlorocarbonate and 2-amino-1-octylethyl vinyl ether give the cyclopentyl ester of 2-rnethyl-5-octyl 1,3 oxazolidone-3-carboxylic acid, also useful as a mosquito repellent.

Example 9 Example 10 By the procedure of Example 1, the following materials are condensed in equimolar ratio:

(a) Dodecyl chlorocarbonate and Z-aminb-l-dodecyl- Equimolar quantities of phenyl chlorocarbonate and Z-aminoethyl vinyl ether are condensed at 40 to 100 C. in the presence of excess potassium carbonate as described in Example 1 and the phenyl ester of 2-methyl-l,3- oxazolidine-3-carboxylic acid is produced.

In place of the phenyl chlorocarbonate there is substituted octylphenyl chlorocarbonate, p-methoxyphenyl chlorocarbonate. p-chlorophenyl chlorocarbonate, pbromophenyl chlorocarbonate, 2,4-dichlorophenyl ch10- rocarbonate and naphthyl chlorocarbonate.

The products are readily isolated by distillation or crystallization and are useful as plant-growth modifiers.

Example 12 (a) 1,6-hexamethylene bis-chlorocarbonate, one mole, and Z-aminoethyl vinyl ether, two moles, are condensed at 40 to 60 in the presence of 1.2 moles of potassium carbonate, 120 ml. of water and 300 ml. of toluene. The product is isolated by distillation and corresponds to the bis-oxazolidine derivative having the structure of Formula VI.

(VI) IMG 0112 (CHn)rO ON 0 OH This compound is useful as a plasticizer for cellulose acetate or butyrate and for copolymers of acrylonitrile, such as those containing 75 parts of acrylonitrile and 25 parts of ethyl acylate.

(b) Similarly, the bis-chlorocarbonate of diethylene glycol is condensed with 3-aminopropyl vinyl ether as described above to yield the bis-tetrahydro-1,3-oxazine derivative having the structure of Formula VII.

(VII) H:

2C (FF: 0 CHzCHz OCON 0 (c) A tris-oxazolidine is obtained by condensing one mole of the tris-chlorocarbonate of 1,1,1-trimethylol ethane with three moles of 2-amino-1-methylethyl vinyl ether. This material is useful as an additive to watersoluble urea-formaldehyde condensates such as those used for the treatment of textiles, paper or plywood. Upon acid catalysis, a rapid cure occurs and the product shows greatly improved water-resistance and substantivity to cellulosic-type substrates.

(d) The tetra-chlorocarbonate of pentaerythritol is condensed by the procedure of this example with four moles of Z-arninoethyl vinyl ether to yield the tetrai0 oxazolidine derivative having the structure of Formula VIII.

(VIII)- HglE-CH: CCH2OCON o 6 111 CH:

This compound is a very viscous oil useful as a plasticizer for cellulose esters such as the acetate or butyrate.

Example 13 (a) The bis-chlorocarbonate derived from hydroquinone is reacted with two moles of Z-aminobutyl vinyl ether by the procedure of Example 1.

(b) The bis-chlorocarbonate of 1,4-dimethylolbenzene is condensed with 2 moles of 2-amino-l-cyclohexylethyl vinyl ether at 50 to C. in the presence of sodium carbonate, water and xylene to yield the bis-oxazolidine derivative having the structure of Formula IX in which 1,4-C H with the attached -CH groups is the divalent p-xylylene radical.

1,4CuH4 CH2OCON O (c) The bis-chlorocarbonate of 2,6-dihydroxynaphthalene is condensed at 50 to 100 C. with two moles of 2-aminoethyl vinyl ether as described in part (b) hereof.

It is to be understood that changes and variations may be made without departing from the spirit and scope of the invention as defined in the appended claims.

I claim:

1. A method comprising reacting an amine having the with a compound selected from the group consisting of those having one of Formulas III and IV:

(III) R OCOCl (IV) B(OCOCl)e and recovering a compound selected from the group consisting of those having one of Formulas I and II:

(II) He 0 \NCOO B the symbols in Formulas I through V being as follows:

n is an integer having a value of l to 2,

x is an integer having a value of 2 to 4,

R is selected from the group consisting of hydrogen, cyclohexyl, vinyl and alkyl groups having 1 to 16 carbon atoms,

R is selected from the group consisting of hydrogen and alkyl groups having 1 to 4 carbon atoms,

R is selected from the group consisting of hydrogen and methyl,

R is selected from the group consisting of hydrogen and methyl,

11 R is-sclectedfrorn the group consisting of hydrogen and alkyl groups having 1 to 4 carbon atoms,

R is selected from the group consisting of saturated and ethylenically unsaturated aliphatic and alicyclic hydrocarbon groups having 1 to 24 carbon atoms; aryl, haloaryl, alkaryl and aralkyl hydrocarbon groups having 6 to 24 carbon atoms, alkoxyalkyl, alkoxyphenyl, and alkylthioalkyl groups having 3 to 24 carbon atoms; and

B is selected from the group consisting of straightchain; branched-chain and cyclic alkylene groups having 2 to 18 carbon atoms; triand tetra-valent aliphatic hydrocarbon groups having 3 to 18 carbon atoms; alkyleneoxyalkylene groups having 4 to 18 carbon atoms; and divalent residues of a substance selected from the group consisting of benzene, naphthalene, and xylylene.

2. A method as defined in claim 1 in which the reaction is effected at a temperature between about 10 C.

- 1-2 and. 100.C. in .the presence of, a basic acceptor for a hydrogen halide.

3. A method as defined in claim 1 in which the reaction is effected at a temperature between about 10 C. and 100 C. in the presence of a basic acceptor for a hydrogen halide and in the presence of an inert solvent.

References Cited in the file of this patent UNITED STATES PATENTS Schlack July 27, 1944 OTHER REFERENCES 

1. A METHOD COMPRISING REACTING AN AMINE HAVING THE FORMULA V: 